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Publication numberUS2756194 A
Publication typeGrant
Publication dateJul 24, 1956
Filing dateMay 7, 1951
Priority dateMay 7, 1951
Publication numberUS 2756194 A, US 2756194A, US-A-2756194, US2756194 A, US2756194A
InventorsBertrand J Mayland
Original AssigneePhillips Petroleum Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Process using nickel carbonyl in hydrogenation, desulfurization, and gasification of carbonaceous materials
US 2756194 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

United States Patent PROCESS USING NICKEL CARBONYL IN HYDRO- GENATION, DESULFURIZATION, AND GASIFI- CATION OF CARBONACEOUS MATERIALS Bertrand J. Mayland, Bartlesville, kla., assignor to Phillips Petroleum Company, a corporation of Delaware Application May 7, 1951, Serial No. 224,917

17 Claims. (Cl. 19653) This invention relates to an improved process for making synthesis gas or fuel gas by gasification of carboncontaining materials. In one aspect this invention relates to an improved process for making fuel gas or synthesis gas from high sulfur carbon-containing material wherein the sulfur content is reduced, by mild hydrogenation. In another aspect this invention relates to an improved process for liquefying coal or upgrading residuum by hydrogenation with the hydrogen being prepared by gasification of the residuum. In still another aspect this invention relates to a novel method for using and recovering a catalyst in the conversion of carbonaceous materials into gases.

In the conversion of carbon-containing materials into gases, a high temperature, long contact time or a catalyst are required. The first requires an excess of oxygen and results in loss of carbon in the feed to carbon dioxide and the second requires excessive reactor size. The present invention involves the use of nickel carbonyl as a catalyst to reduce the residual hydrocarbon to an equilibrium value.

In this invention, oil containing dissolved nickel carbonyl is sprayed into a combustion chamber together with steam and oxygen. At the temperature of combustion the nickel carbonyl is decomposed to elemental nickel which is finely dispersed throughout the products of initial combustion and acts as a catalyst for reforming residual hydrocarbons. The reactions products are cooled by quenching to a point where nickel carbonyl reforms and then it is scrubbed from the gases by the fresh liquid hydrocarbon and reused.

In the hydrogen of coal, part of the pasting oil containing dissolved nickel carbonyl may be diverted to a hydrogenation step wherein a mild hydrogenation of coal or of other carbonaceous materials may be accomplished. The coal is mixed with pasting oil containing nickel carbonyl and the mixture preheated wherein the nickel carbonyl is decomposed to elemental nickel. The slurry is then contacted with hydrogen at an elevated pressure in the hydrogenation zone. A portion of the coal is liquefied and the sulfur in the coal is converted to hydrogen sulfide. The hydrogenated coal and catalyst slurry is passed to a separation zone to remove hydrogen sulfide and liquid product. The residual slurry together with nickel catalyst is taken through a gasification process as previously described.

Because the sulfur content of coals may be as high as per cent by weight or more, fuel gas or synthesis gas made by conventional coal gasification processes is in many cases high in sulfur, which is undesirable for various reasons such as corrosion, catalyst poisoning, gum formation, etc. Sulfur compounds may be removed from the gas by many methods including physical absorption and chemical reaction but because of the volume of the gas stream and the presence of high carbon dioxide content, the methods are expensive.

The removal of sulfur before gasification in this invention overcomes the previous difiiculties just mentioned.

Referring to the drawing a residual hydrocarbon oil is introduced through a line 32 containing valve 36 to the scrubber 30. Nickel carbonyl contained in a. gas mixture formed in the process is admitted to the scrubber 30 from line 37 and is dissolved in the oil. The residual hydrocarbon oil containing usually less than 1.0 per cent by weight of nickel carbonyl based on the feed stock, and preferably between 0.1 and 0.5 per cent by weight, is passed through line 31 and line 26. This mixture is sprayed into the gasification chamber 29 together with oxygen from line 27 and steam from line 28. At the tem' perature of combustion the nickel carbonyl is decomposed to elemental, nickel which is finely dispersed throughout the products of initial combustion and acts as a catalyst for reforming residual hydrocarbons. Typical operating conditions for the gasification process are:

Broad Range Preferred Range Temperature, F 1,400 to 3,000.- 1,800 to 2,000. Pressure, atms 1 to 20 2 to 7. Contact time, seconds 0.1 to 10 1 t0 6.

The reaction products are: methane, water, carbon dioxide, carbon monoxide and hydrogen. A typical analysis may be as follows:

Mol percent The reaction products are cooled for example by water quenching, to a point where nickel-carbonyl reforms and then it is scrubbed from the gases in the scrubber 30 by the fresh liquid hydrocarbon feed from line 32 and reused in the gasification step by recycling through line 31. The nickel is converted to nickel carbonyl in the presence of carbon monoxide at temperatures of 200 to 300 F. in a suitable reaction chamber prior to removal of ash.

A cyclone separator (not shown) is placed in line 37 after the water quench to remove the ash through line 39. Carbon monoxide and hydrogen-containing gas are withdrawn from the scrubber 30 through line 33 to outside utilization through line 34 containing valve 38, or a portion of this gas may be conducted to a water gas shift reaction step 35 to produce a high hydrogen content gas. The high hydrogen content gas is conducted through line 13 and line 14 to the hydrogenation step 15 to be described subsequently. V

A mild hydrogenation of coal may be accomplished using nickel as a catalyst obtained by the decomposition of nickel carbonyl. The process is described with respect to coal but it can be readily modified for other carboncontaining materials such as ground oil shale, shale oil, refinery residuums, etc. In preparing the coal or other carbonaceous material for hydrogenation, it is desirable to pulverize to a relatively fine state of sub-division, preferably such that it will pass through a standard Tyler screen of about mesh. The powdered coal is treated by conventional mechanical separation methods to remove inorganic sulfur. After being pulverized, the coal is conducted through feed line 10 to chamber 11. In chamber 11, the coal is admixed with a pasting oil from line 12 containing usually less than 1.0 per cent by weight of nickel carbonyl based on the carbonaceous material. This pasting oil is a recycle oil produced in the process as will be described. In general from one to three parts of pasting oil per part of coal provides a suitable fluid consistency for reaction. In general, about 0.01 to 1.0 per cent and preferably between 0.1 and 0.5 per cent by weight of the nickel catalyst based on the carbonaceous material is a sufficient amount.

P hm

Broad Range Temperature, F. Pressure, atmospheres o ta time u Hydrogemcu. it. perl Th nick carhquy is 'de omuqscsi to e em ta ickel in the preheater, and the elemental nickel acts as the catalystih he hydro e tion acacia Th y r ted shalom? the catal t ur i with: drawn from the hydrogenation zone 15, and passed through line 16 to a separation zone 17. Hydrogen-rich gas is taken off through line 18, and recycled to the hydrogenation step. Light gases and hydrogen sulfide are taken off through line 19. The gasoline fraction boiling below 400 to 430 F. is separated from the remaining heavyoil slurry. The gasoline fraction is taken off through line 20. The heavy-oil slurry boiling above 400 to 430 F. is withdrawn from the separation zone 17 and passed through line 21 to a steam distillation unit 22, with steam being admitted through line 23. The heavy-oil slurry is steam distilledto obtain'a pasting oil fraction taken ofi through line 24 and a residual slurry taken off through line 25. The pasting oil fraction is passed through line 24 to a separation zone-40 where water is taken 011 through line 41. The pasting oil iswithdrawnfrom the separation zne40 through line 42 and passed to a scrubber 30. Exs pasti g o not rcqvi cd or e Pro s can bcwit drawn t r i h li e 4.

h residual slur y w h hs th nic l cata y t rom the ste m d t l t on it 22 i t kcu of hrou h line and passed to line 26. Part of the pasting oil containing dissolved nickel ca o yl f om in 114 3 e d v r e into line 26 and there admixed with the residual slurry Order o t i ch consist nc sui able for spraying into the gasification chamber. The gasification process has been previously described.

a at on and mod ficat on a e P9$ i 1i within th c p of h SPWificatiQh! dr win s and t e appended cl ims to h s n ntichr hs. s s ccs whishi a method for decompo i g n kel ca bonyl a act on one to form e menta hicks! a a c t lys fo h eac n an cooling th 'fl'il iiflll Products to refo m n ck l carb nyl and so ing he r rmed hi ks! carbony in the liquid hydrocarbon which comprises the fresh feed toithe rgag: don-zone. a

I claim:

1- The p ocess o co ve in a a bo o ta ni inc rihl into liqui y ocarbo s oilih in h asolin ran e and ages containing garbon monoxide and hydrogen which comp s passing a d carbon pas i i cohns nickel ca bo yl n dm x ure wi ydro e and a c i mwutaihi g mate ia i o a hy en on zo e; maintaining herei a hyihss h t ch ac ion at; stamps;- fliurc suflicic i ..iP9 n ckel arbony tcnicke an a o m no ide an to hyiirg ha c a e s a PM- rim i bo mh hia hs mate l; sep at n a d to ring l q d d o ah hh r oil n i the aso ine ch ch b h s as to disso eucts containing substantial amounts of carbon monoxide and hydrogen, and to convert the nickel carbonyl into nickel and carbon monoxide; cooling said gaseous products so as to convert nickel and carbon monoxide into nickel carbonyl as a vapor; passing said gaseous product into contact with said pasting oil overhead product so as to remove nickel carbonyl from said gaseous product by dis solution in said pasting oil as hercinbefore set forth; recovering a portion of said gaseous product as a product of the process; passing the remaining portion of said gaseous product to a Water gas shift reaction so as to produce a gas having a high hydrogen content; and passing said gas having a high hydrogen content to said hydrogenation zone.

2. The process of claim 1 wherein the amount of nickel carbonyl is maintained in the range 0.1 to 1 weight per cent based on the pasting oil; the hydrogenation reaction is maintained at a temperature in the range 750 to 1000 F., a, pr sure in the range to 700 atmospheres, a contact time of 0,25 (no.8 hours and a hydrogen content of 5 to Z Scnbic feet pen pound; Of charge stock; the gasification reagtion is maintainedat a temperature in the range 1400 to, 30 0O R, a pressure in the range 1 to 20 atmospheres, and with a contagt time in the range 0.1 to 10 seconds; and the temperature to which the gaseous products of asificaiich ar -cooled i below F- 3. The process of claim 1 wherein the amount of nickel carbonyl is maintained in the range of 0.1 to 0.5 weight per gent based on the pasting oil; the hydrogenation reaction is maintained at a temperature in the range 800 to 900 R, a pressure in the range 350 to 550 atmospheres, a contact time of 1 to 3 hours and a hydrogen content of 10 to 15 cubic feet per pound of charge stock; the gasification reaction is maintained at a temperature in the range 1800 to 2 000 E, a pressure in the range 2 to 7 atmospheres and with a contact time in the range 1 to 5 secends; and the temperature to which the gaseous products of gasilication are cooled is in the range 200 to 300 F.

.4. The process of claim 3 wherein the carbon-containi s materi l i coa "5. The process of claim 1 wherein the carbon-contains-m erial is oa 6. The process of claim 1 wherein the carbon-containns mater l is oilv s al 7. The process of claim 1 wherein the carbon-containh hihtcr al is re ne r s 8. The process ofconverting a sulfur-containing carbonaceous mater al into liquid hydrocarbons, boiling in h so in nge a a a nta ni y r g a d carbon monoxide which comprises passing a hydrocarbon pasting oil, containing nickel carbonyl, in admixture with a sulfur-containing carbonaceous material and hydrogen into a hydrogenation zone; maintaining therein a hydrogenation reaction at a temperature sufiicient to decomposensaid nickel carbonyl to nickel and carbon monoxide, to hydrogenate at least a portion of said carbonacsc ate ial o h droca b ns n t s tc said ul u io yd ac ulfi e; sepa mo hydrogen sulfi de from the system; separating and recovering liquid hydrocarbons, boiling in the gasoline range, as a product of the process; steam distilling a remaining heavy oil so-as to obtain a pasting oil overhead product and a residuum, containing said nickel, as the bottoms product; passing said pasting oil into contact with a gaseous stream containing nickel carbonyl so as to dissolve nickel carhonvl i h P ti o l; adm x portion o a d pas oil; containing nickel carbonyl with said residuum and with steam and oxygen; subjecting the resulting mixture to, gasification reaction conditions of temperature and pre sure so as IQSUbS' W Q Y n e ixtu e into gaseous products containing substantial amounts of carbon monoxide and hydrogen, and to convert the nickel carbonyl into nickel and carbon monoxide; cooling said gaseous produ ctsiso as to convert the nickel and carbon monoxide into nickel carbonyl as a vapor; passing said all A Ml ll I gaseous product into contact with said pasting oil overhead product so as to remove nickel carbonyl from said gaseous product by dissolution in said pasting oil as hereinbefore set forth; recovering a portion of said gaseous product as a product of the process; passing the remaining portion of said gaseous product to a water gas shift reaction so as to produce a gas having a high hydrogen content; and passing said gas having a high hydrogen content to said hydrogenation zone.

9. The process of claim 8 wherein the amount of nickel carbonyl is maintained in the range 0.1 to 1 weight per cent based on the pasting oil; the hydrogenation reaction is maintained at a temperature in the range 750 to 1000 F., a pressure in the range 70 to 700 atmopheres, a contact time of 0.25 to 8 hours and a hydrogen content of 5 to 25 cubic feet per pound of charge stock; the gasification reaction is maintained at a temperature in the range 1400 to 3000 F., a pressure in the range 1 to 20 atmospheres, and with a contact time in the range 0.1 to seconds; and the temperature to which the gaseous products of gasification are cooled is below 300 F.

10. The process of claim 8 wherein the amount of nickel carbonyl is maintained in the range of 0.1 to 0.5 weight per cent based on the pasting oil; the hydrogenation reaction is maintained at a temperature in the range 800 to 900 F., a pressure in the range 350 to 550 atmospheres, a contact time of 1 to 3 hours and a hydrogen content of 10 to cubic feet per pound of charge stock; the gasification reaction is maintained at a temperature in the range 1800 to 2000 F., a pressure in the range 2 to 7 atmospheres and with a contact time in the range 1 to 5 seconds; and the temperature to which the gaseous products of gasification are cooled is in the range 200 to 300 F.

11. The process of claim 10 wherein the carbon-con taining material is coal.

12. The process of claim 8 wherein the carbon-containing material is coal.

13. The process of claim 8 wherein the carbon-containing material is oil shale.

14. The process of claim 8 wherein the carbon-containing material is refinery residuum.

15. In the conversion of a carbon-containing material into a gas containing carbon monoxide and hydrogen in prises passing an admixture of nickel carbonyl, liquid hydrocarbon and a carbon-containing material into a combustion zone together with steam and oxygen, de composing nickel carbonyl to elemental nickel and carbon monoxide by heat of combustion evolved, cooling products of said combustion sufiiciently to reform nickel carbonyl, as a vapor, absorbing said nickel carbonyl from said combustion product gases in a liquid hydrocarbon and passing said liquid hydrocarbon containing said absorbed nickel carbonyl to said combustion zone.

16. The method of claim 15 wherein the amount of nickel carbonyl is maintained in the range 0.1 to 1.0 weight per cent based on the liquid hydrocarbon, the temperature in the combustion zone is maintained in the range 1400 to 3000 F., the pressure is maintained in the range 1 to 20 atmospheres, the contact time is maintained in the range 0.1 to 10 seconds, and the temperature to which the combustion products are cooled is below 300 F.

17. The method of claim 15 wherein the amount of nickel carbonyl is maintained in the range 0.1 to 0.5 weight per cent based on the liquid hydrocarbon, the temperature in the combustion zone is maintained in the range 1800 to 2000 F., the pressure is maintained in the range 2 to 7 atmospheres, the contact time is maintained in the range 1 to 5 seconds, and the temperature to which the combustion products are cooled is in the range 200 to 300 F.

References Cited in the file of this patent UNITED STATES PATENTS 1,138,201 Ellis May 4, 1915 1,251,202 Ellis Dec. 25, 1917 2,167,250 Pferrmann July 25, 1939 2,250,421 Riblett July 22, 1941 2,346,754 Hemminger Apr. 18, 1944 2,579,398 Roetheli Dec. 18, 1951 2,623,058 Mattox Dec. 23, 1952 2,636,841 Mason Apr. 28, 1953 OTHER REFERENCES Mellor: A Comprehensive Treatise on Inorganic and Theoretical Chemistry, vol. 5, page 953. London, Longthe presence of a nickel catalyst, the method which com- 5 mans, Green & 1924-

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
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US1251202 *Feb 6, 1914Dec 25, 1917Carleton EllisCatalyzer-concentrate and process of making same.
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Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US2860101 *Apr 20, 1953Nov 11, 1958Pelipetz Michail GBalanced hydrogenation of coal
US2885337 *Apr 20, 1953May 5, 1959Hydrocarbon Research IncCoal hydrogenation
US3102588 *Jul 24, 1959Sep 3, 1963Phillips Petroleum CoProcess for recovering hydrocarbon from subterranean strata
US3180813 *May 31, 1961Apr 27, 1965Consolidation Coal CoElectrolytic process for producing hydrogen from hydrocarbonaceous gases
US3954596 *Jun 3, 1974May 4, 1976Schroeder Wilburn CProduction of low sulfur heavy oil from coal
US4152248 *May 2, 1978May 1, 1979The United States Of America As Represented By The United States Department Of EnergyHydrogenation of coal liquid utilizing a metal carbonyl catalyst
US4158637 *Apr 30, 1976Jun 19, 1979Westinghouse Electric Corp.Conversion of coal into hydrocarbons
US4224137 *Aug 4, 1978Sep 23, 1980Schroeder Wilburn CRecovery of catalysts from the hydrogenation of coal
US4325802 *Nov 17, 1980Apr 20, 1982Pentanyl Technologies, Inc.Method of liquefaction of carbonaceous materials
US4331530 *Feb 27, 1978May 25, 1982Occidental Research CorporationProcess for the conversion of coal
US4369106 *Mar 16, 1981Jan 18, 1983Exxon Research And Engineering Co.Coal liquefaction process
DE3145622A1 *Nov 17, 1981Sep 2, 1982Pentanyl Tech Inc"verfahren zur verfluessigung von kohlenstoffhaltigen materialien"
Classifications
U.S. Classification208/420, 208/423, 208/112, 48/212
International ClassificationC10G1/08, C10G1/00, C01B3/38
Cooperative ClassificationC01B2203/0465, C01B2203/0415, C01B2203/0877, C10G1/006, C10G1/083, C01B2203/146, C01B2203/1247, C01B2203/04, C01B2203/0244, C01B2203/0844, C01B3/386, C01B2203/065, C10G1/086, C01B2203/1052, C01B2203/142, C01B2203/0283, C01B2203/82
European ClassificationC01B3/38D, C10G1/00D, C10G1/08D, C10G1/08B